24035-36-7

Usage

InChI:InChI=1/C20H30O2/c1-13(2)15-10-14-6-7-18-19(3,4)8-5-9-20(18,12-21)16(14)11-17(15)22/h10-11,13,18,21-22H,5-9,12H2,1-4H3/t18-,20-/m0/s1

Upstream product

• 113801-93-7 (2R,4aR,10aS)-2-Bromo-7-isopropyl-6-methoxy-1,1,4a-trimethyl-1,4,4a,9,10,10a-hexahydro-2H-phenanthren-3-one 
• 83109-84-6 (+/-)-2β,2O-epoxy-12-methoxyabieta-8,11,13-triene 
• 108642-75-7 (4bR,8aS,10aS)-(-)-1,4b,5,6,7,8,8a,9,10,10a-decahydro-4b-methoxymethoxymethyl-8,8-dimethylphenanthren-3(2H)-one 
• 108642-70-2 (4aS,8aS)-(+)3,4,4a,7,8,8a-hexahydro-8a-methoxymethoxymethyl-5,5-dimethylnaphthalene-1,6(2H,5H)-dione 1-ethylene acetal 
• 108642-72-4 (4aS,8aS)-(-)-3,4,4a,5,6,7,8,8a-octahydro-8a-methoxymethoxymethyl-5,5-dimethylnaphthalen-1(2H)-one 
• 108642-71-3 C₁₇H₃₀O₄ 
• 98770-79-7 (S)-5,5-(ethylenedioxy)-2,3,4,4a,5,6,7,8-octahydro-4a-<(methoxymethoxy)methyl>-1-methylnaphthalene-2-one 
• 87315-71-7 20-acetoxy-12-acetylabieta-8,11,13-triene 
• 87315-73-9 20-acetoxy-12-acetyl-5βH-abieta-8,11,13-triene 
• 87315-68-2 20-acetoxyabieta-8,11,13-triene 
• 87315-68-2 20-acetoxy-5βH-abieta-8,11,13-triene 
• 87315-68-2 Acetic acid (R)-7-isopropyl-1,1-dimethyl-1,3,4,9,10,10a-hexahydro-2H-phenanthren-4a-ylmethyl ester 
• 87315-69-3 abieta-8,11,13-trien-20-ol 
• 87315-70-6 5βH-abieta-8,11,13-trien-20-ol 

Downstream Products

• 113801-92-6 (4aS,10aR)-7-Isopropyl-6-methoxy-1,1-dimethyl-9-(toluene-4-sulfonyloxy)-1,3,4,9,10,10a-hexahydro-2H-phenanthrene-4a-carboxylic acid methyl ester 
• 67494-15-9 (+/-)-pisiferic acid 
• 514-62-5 ferruginol 
• 99152-16-6 9(10->20)abeo-abieta-5(10),8,11,13-tetraene-12-ol 
• 76210-23-6 pisiferin 
• 97403-22-0 (-)-isopisiferin 

Relevant academic research and scientific papers

ANTIFUNGAL ACTIVITY OF PISIFERIC ACID DERIVATIVES AGAINST THE RICE BLAST FUNGUS

Twenty-eight derivatives of pisiferic acid (1), an antifungal constituent of Chamaecyparis pisifera var. plumosa against Pyricularia oryzae, were prepared and tested for activity.The size of the substituents at C-10 and C-12, as well as the presence and electronegativity of the constituent oxygen atoms, were inferred to be structural determinants for the activity of pisiferic acid derivatives.A computer graphic comparison between the derivates and probenazole (35) (a commercial antifungal agent of the fungus) revealed the similarity of the size and location of the oxigen-containing substituents, which was supported by the similar mode of action of 1 and 35.Key Word Index - Chamaecyparis pisifera var. plumosa; Cupressaceae; antifungal activity; structure-activity; computer graphic; pisiferic acid; probenazole.

The Synthesis of (+)-Pisiferol and (+)-Pisiferal

Reduction of abieta-8,11,13-trien-6-one with lithium aluminium hydride, followed by treatment with lead tetraacetate and iodine, afforded 6β,20-epoxyabieta-8,11,13-triene.This was converted into a separable mixture of abieta-8,11,13-trien-20-ol (13) and 5βH-abieta-8,11,13-trien-20-ol (14) by a series of reactions; ether cleavage with acetic p-toluenesulfonic anhydride, catalytic hydrogenation, and reduction with lithium aluminium hydride.Acetylation of 13 and 14 gave the corresponding acetates, 20-acetoxyabieta-8,11,13-triene (11) and 20-acetoxy-5βH-abieta-8,11,13-triene (12).Friedel-Crafts acylation of 11 with acetyl chloride in the presence of anhydrous aluminium chloride afforded 20-acetoxy-12-acetylabieta-8,11,13-triene, which was converted into pisiferol by oxidation with m-chloroperbenzoic acid and subsequent treatment with lithium aluminium hydride.The synthetic pisiferol was oxidized with Jones reagent to give pisiferal.Similarly, 5βH-abieta-8,11,13-triene-12,20-diol was synthesized from 12.Conversion of the cis A/B ring junctions in 12 into the trans ones is also described.

Stereocontrolled total synthesis of (±)-pisiferol and (±)-pisiferal

The stereoselective total synthesis of (±)-pisiferol (1) and (±)-pisiferal (2) has been successfully accomplished using the trans-octahydrophenanthrene derivative 20 as a key intermediate. Intramolecular cyclisation of the diazoketone 15 followed by catalytic hydrogenation provided, stereoselectively, the keto-ester 17 which was converted into the acetate 20 through the intermediates 18 and 19.

Total Synthesis of (+/-)-Pisiferic Acid

A total synthesis of (+/-)-pisiferic acid (1) has been achieved by utilising the keto ether (22) which, in turn, was prepared from the alcohol (14).Subjection of the keto ether (22) to three sequential reactions (formylation, Michael addition with methyl vinyl ketone, and intramolecular aldol condensation) provided the tricyclic ether (27) whose conversion into the methoxyabietatriene (32) was accomplished in four steps (ethoxycarbonylation, Grignard reaction with methyl-lithium, acid-catalysed dehydration, and methoxylation).Reaction of the methoxyabietatriene (32) with zinc, zinc iodide, and acetic acid produced (+/-)-pisiferol (2) which was finally converted into (+/-)-pisiferic acid (1).The ketone (34) was converted into the abietatriene (41) following exactly the same procedure adopted for the transformation of the keto ether (22) into the abietatriene (32).Hydroboration-oxidation of (41) followed by oxidation with Jones reagent and reduction with lithium aluminium hydride followed by transannular oxidation gave the abietatriene (36).

SYNTHESIS OF (+/-)-2β,2O-EPOXY-12-METHOXYABIETA-8,11,13-TRIENE

The synthesis of the titled compound (1) and its conversion to pisiferic acid (2) are described.

A Total Synthesis of (+)-Pisiferol

A total synthesis of (+)-pisiferol (1) has been accomplished by utilising an optically active Wieland-Miescher ketone analogue (S)-(+)-(6) bearing an angular protected hydroxymethyl group, as the key intermediate.Reductive methylation of the monoacetal (7) of compound (6), followed by Huang-Minlon reduction, gives the trans-decalone acetal (9).Construction of the remaining carbocycle leading to the dodecahydrophenanthrenone (14) is achieved through five sequential reactions (deprotection, methoxycarbonylation, Michael addition with methyl vinyl ketone, demethoxycarbonylation, and intramolecular aldol cyclisation).After introduction of the 2-hydroxypropan-2-yl side-chain, dehydration followed by base-catalysed aromatisation affords pisiferol methoxymethyl ether (18).Finally, hydrolysis furnishes (+)-pisiferol (1).

Total Synthesis of (+/-)-Pisiferic Acid, Methyl (+/-)-Pisiferate, and (+/-)-Pisiferol

Acid catalyzed cyclization of 4-(3-isopropyl-4-methoxyphenethyl)-3,5,5-trimethyl-2-cyclohexen-1-one afforded 12-methoxyabieta-8,11,13-trien-2-one and its cis-isomer.Both compounds were further converted into 12-methoxyabieta-8,11,13-trien-2β-ol, which was treated with lead tetraacetate in the presence of iodine to yield 2β,20-epoxy-12-methoxyabieta-8,11,13-triene.Ether cleavage of the 2β,20-epoxy compound with acetyl p-toluenesulfonate, followed by catalytic hydrogenation, afforded 20-acetoxy-12-methoxyabieta-8,11,13-triene (23).This was then converted into methyl 12-methoxyabieta-8,11,13-trien-20-oate (27) via methyl 12-methoxy-7-oxoabieta-8,11,13-trien-20-oate.Demethylation of 27 with AlBr3-EtSH gave pisiferic acid, but with AlCl3EtSH 27 was partially demethylated to give methyl pisiferate.The acetate 23 was also converted into pisiferol by demethylation and reduction